Patent GB-1039379-A (GB)
Title: Reactive dyestuffs containing a quinoxaline nucleus
Inventor: BOOTH GERALD
Filed: 1963-09-23
Abstract: The invention comprises dyestuffs containing attached to a carbon atom present in the dyestuffs at least one group of the formula <FORM:1039379/C4-C5/1> wherein R represents hydrogen or C1 to C4 alkyl; X represents Cl or Br or -SO3M wherein M represents Na or K; and the benzene ring A may contain further substituents.  Each of the groups of the above formula is attached to a carbon atom present in the dyestuffs.  The said carbon atom may form part of an aryl residue present in the dyestuffs or may form part of an alkyl chain which is directly attached to an aryl residue present in the dyestuffs or is attached to an aryl residue through a bridging atom or group.  The dyestuffs may be dyestuffs of the azo, nitro, anthraquinone or phthalocyanine series; and may contain co-ordinately bound metal atoms.  They also preferably contain at least one water-solubilizing group.  The dyestuffs containing groups of the above formula, wherein X represents Cl or Br may be obtained by reacting a dyestuff compound which contains at least one -NHR group with a compound of the formula <FORM:1039379/C4-C5/2> wherein X1 represents Cl or Br (see Division C2 for preparation) at least one molecular proportion of the said compound being used for each -NHR group present in the dyestuff compound. The dyestuffs containing groups of the above general formula wherein X represents -SO3M may be obtained by reacting a dyestuff wherein X represents Cl or Br with a Na or K salt of sulphurous acid.  Specified examples of dyestuffs containing at least one -NHR group are as follows: (1) Monoazo compounds of the formula <FORM:1039379/C4-C5/3> wherein D1 represents a mono- or di-cyclic aryl radical which is free from azo groups and NHR groups.  (2) Disazo compounds of Formula III, wherein D1 represents a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series and the naphthalene nucleus is substituted by the NHR group.  (3) Monoazo compounds of the formula <FORM:1039379/C4-C5/4> wherein D1 represents a mono or dicyclic aryl radical as defined in class (1) and the benzene nucleus may contain halogen atoms, alkyl, alkoxy, carboxylic acid or acylamino groups. (4) Mono- or dis-azo compounds of the formula <FORM:1039379/C4-C5/5> wherein D1 represents a radical as defined for class (2) or a mono- or dicyclicarylene radical of the benzene or naphthalene series and K represents the radical of a naphthol sulphonic acid or the radical of an enolized or enolizable ketomethylene compound having the OH group oto the azo group.  (5) Mono- or dis-azo compounds of the formula D1-N = N-K2-NHR wherein D1 is as defined in classes (1) and (2), K2 represents the radical of an enolizable ketomethylene compound having the -OH group oto the azo group.  (6) The metal complex compounds of dyes of Formulae III, V and VI which contain a metallizable group ortho to the azo group in D1.  (7) Anthraquinone compounds of the formula <FORM:1039379/C4-C5/6> wherein the anthraquinone nucleus may contain an additional SO3H group in the 5-, 6-, 7- or 8-position and Y represents a bridging group which is preferably a divalent radical of the benzene series.  (8) Phthalocyanine compounds of the formula <FORM:1039379/C4-C5/7> wherein Pc represents the phthalocyanine nucleus preferably of copper phthalocyanine, o  represents -OH and/or NH2 or substituted amino, Y1 represents a bridging group preferably an aliphatic, cycloaliphatic or aromatic bridging group, n and m each represent a value of from 1 to 3 and may be the same or different provided that n+m is not greater than 4.  (9) Nitro dyestuffs of the formula O2N-B1-NH-B2-NHR wherein B1 and B2 represent monocyclic aryl nuclei, the nitro group in B1 being ortho to the NH group.  The dyestuffs can also be obtained by reacting dyestuff intermediates containing reactive halogen atoms, such as 1-amino-4-bromo - anthraquinone - 2 - sulphonic acid or phthalocyanine sulphonylchlorides can be reacted with amines containing a group of Formula I, such as an amine of the formula <FORM:1039379/C4-C5/8> wherein the benzene ring A1 can be substituted by halogen, methyl, methoxy or sulphonic acid groups.  The dyestuffs can also be obtained by diazotizing a primary aromatic amine and coupling the resulting diazo compound with a coupling component, the primary aromatic amine and the coupling component together containing at least one group of Formula I.  A preferred class of the dyestuffs are those of the formula <FORM:1039379/C4-C5/9> wherein p represents 1 or 2, and D5 represents a dyestuff radical of the azo, anthraquinone or phthalocyanine series which contains at least one -SO3H or -COOH group.  The dyestuffs may be applied to natural and artificial textile materials, for example, cotton, viscose rayon, regenerated cellulose, wool, silk, cellulose acetate, polyamides, polyacrylonitrile, modified polyacrylonitrile and aromatic polyester fibres, by dyeing, padding or printing processes, whereby the textile materials are coloured in bright shades (see Division D1 for dyeing processes).ALSO:Compounds of the formula <FORM:1039379/C2/1> II wherein X1 represents Cl or Br and the benzene ring A may contain further substituents such as chlorine, alkyl, alkoxy and nitro groups, are obtained by treating the corresponding compound wherein X1 represents an -OH group with a chlorinating or brominating agent, for example POCl3, POBr3, PCl5 or PBr5. Compounds of the formula <FORM:1039379/C2/2> VII wherein R is H or C1-C4 alkyl and X is Cl, Br or SO3M, and the benzene ring A1 may be substituted by halogen, methyl, methoxy or sulphonic groups, are obtained by reacting the corresponding amino- or nitro-benzene containing a -NHR group with a compound of Formula II, and subsequently reducing the nitro group to an amino group.ALSO:Dyestuffs containing at least one group of the formula <FORM:1039379/D1-D2/1> wherein R represents hydrogen or C1 to C4 alkyl; X represents Cl or Br or -SO3M wherein M represents Na or K; and the benzene ring A may contain further substituents (see Division C4 for preparation), are applied to natural and artificial textile materials for example, cotton, viscose rayon regenerated cellulose, wool, silk, cellulose acetate, polyamides, polyacrylonitrile, modified polyacrylonitrile and aromatic polyester fibres by dyeing, padding or printing processes. Dyestuffs containing water-solubilizing groups may be applied to cellulose textiles in conjunction with an acid-binding agent.  The aqueous solution of one or more of the said dyestuffs may also contain substances which are known to assist the application of dyestuffs to textile materials. The cellulose textile materials can be printed with a printing paste containing one or more of the said dyestuffs.  This may be brought about by pretreating the cellulose textile material with acid-binding agent, by incorporating an acid-binding agent in the printing paste, by applying the printing paste and subsequently immersing the textile material in a hot aqueous solution or suspension of the acid-binding agent or the printed textile material impregnated with an aqueous solution or suspension of the acid binding agent. At the conclusion of the dyeing and/or printing process the so-coloured cellulose textiles may be subjected to a "soaping" treatment.  Dyestuffs not containing water-solubilizing groups are applied to textiles in the form of an aqueous dispersion which may be obtained by gravel-milling the dyestuff with water in the presence of a dispersing agent.  The dyestuffs may be applied to nitrogen-containing textiles such as wool and polyamide textiles, from a mildly alkaline, neutral or acid dyebath.